DE1770542A1 - Base compounds based on epoxy compounds - Google Patents

Description

base compounds on the basis of Epoxydver
bindings

The invention relates to base materials based on liquid epoxy compounds or "epoxy resins" which are known as "multipurpose resins" can be used for a wide variety of uses and which can be stored for long periods of time without crystallization, especially at ordinary temperatures, or ordinary winter temperatures »

The epoxy compounds known as "epoxy resins", the
are liquid at ambient temperature, are often used in particular as casting resins for the production of laminatesj as insulating materials for electrical conductors, as binders in solvent-free paints and varnishes and as adhesives. In these types of applications, the viscosity of the resins is usually adjusted. Pure production

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1098U / 1768

A low viscosity is desirable for clay laminates, while higher viscosities appear more suitable for adhesives, foams and solvent-free paints. The flowability of the resin is important for casting purposes and for the production of casings, but low volatility is also required to avoid the formation of gas bubbles or even foams, especially during casting operations in a vacuum _{e is the} subject of the invention the creation of liquid base materials on the basis of epoxy compounds (epoxy resins ^, as "multipurpose resins" with a viscosity suitable for a wide range of applications, which can be lowered for special purposes, if desired, by adding further diluents. Another object of the invention is the Creation of liquid epoxy resin compounds with low volatility <,

Liquid polyglycidyl ethers of DiphenylolpiOpan (im hereinafter referred to as DPi) are the most widely used liquid epoxy resins.

These liquid Polyglyöidyläthe * are HafiSe YGÄ low Molecular weight obtained by dissolving DPP in a large

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Excess of epichlorohydrin, usually 10 moles of epichlorohydrin per mole of DPP and addition of aqueous alkali metal hydroxide are produced at elevated temperature, with a reaction takes place and then the formed

and
Salt, the water / an excess of Bpichlorhydrxnuß are stripped off and the resin is isolated as a viscous liquid. The main component of such a resin is the diglycidyl ether of DPP, which is represented by the formula

OH ₉ OH-OH ₉ 0-R-0-GH ₉ OH-OH

S2 ² \

₉₉ H ₉ ² \ /

0 'V

in which R is the bilateral hydrocarbon residue of DPP.

A disadvantage of these resins is that they crystallize when stored at room temperature or below can occur, which greatly reduces the flowability. j

Attempts have already been made to prevent the crystallization of liquid polyglycidyl ethers of DPP by additives or to delay. Although in some respects obsolescence could be achieved, in others it remained There are still disadvantages. While the tendency to crystallize could be suppressed, achieved the volatility of the resin and / or the temperature value of the deformation in the heat and / or the strength

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The ability of the hardened object to be often undesirable values to create the liquid polyglycidyl ethers of DPP and contain essentially all the desired properties including a low viscosity and volatility without, or at least, their tendency to crystallize less tendency to crystallize under normal storage conditions and to create hardened objects provide which have a high heat distortion temperature.

The basic compositions according to the invention based on
Epoxide compounds having a viscosity between 90 and 150 poises at 25 ° G, preferably, not more than 150 poises and an Flüchtigkeitsgehalt of less than ₈ O 3 wt. ^, In particular not more than 0.2% by weight. Dadurcbfeekennzeichnet that it consists of ( A) consists of a liquid polyglycidyl ether of DPP, which is obtained by reacting
4-8 mol equivalent of epichlorohydrin with one mol equivalent of DPP in the presence of an alkaline compound has been prepared and as the second component (B)
0.5-10% by weight, based on the polyglycidyl ether of DPP, of a liquid epoxide with a viscosity below 20 poises at 25 ⁰ O and a volatility value below 25, the volatile epoxide from the group of glyeidyl

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esters of monocarboxylic acids with at least 12 carbon atoms per molecule, the glycidyl ester of polycarboxylic acids and the glyoidyl ether is selected from polyhydric alcohols o

In this context, "liquid * ¹ " means the liquid state at 25 0 than the temperature usually used to determine physical properties. G

The Flüohtigkeitsgehalt, according DIK 16945, sheet 1, sub 4.8, August I966 certain Here, a sample of 5 g of 3 hours at 140 ⁰ G heated "The percent weight loss is the Flüohtigkeitsgehalt. The volatility value corresponds to the numerical value of Vo - Vr e ^ Qq where Vc is the volatility content of the

Is mass containing component (B), Vr = the volatility content of the polyglycidyl ether of DPP as | such and D «denotes the concentration of component (B) in percent by weight, based on the polyglycidyl ether from DPP is.

The liquid polyglycidyl ether of DPP, which according to the invention Used in the basic masses is made by repositioning of Bpiohlorhydrin with DPP in a molar ratio between 4i1 and 81I, for example 7: 1 in the presence of a obtained alkaline compound.

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The alkaline medium which is used for the dehydrohalogenation of the chlorohydrin ether is created using basic substances such as sodium or potassium hydroxide, preferably in a stoichiometric excess such as an excess of 5-10 mol, based on the content of phenolic hydroxyl groups in the DPP. The alkali can be added in the form of an aqueous solution of, for example, 20-50%. If desired, solvents such as methylobutyl ketone or isopropyl alcohol can be used. The reaction is preferably conducted at temperatures in the range \ * on 50 "x 150 ⁰ O The alkali may be carried out before the Keaktionsgemisoh be added during or after mixing of Epiohlorhydrin and DPP. The aqueous alkaline solution is preferably added gradually, for example over a period of 2-4 hours, to a solution of DPP epichlorohydrin, the added water being distilled off azeotropically by means of the excess epichlorohydrin. After the aqueous layer of the condensate has been separated off, the epiohlorohydrin can be returned to the reactor. During the reaction, the participants in the reaction should be appropriately touched, so that sufficient contact between the aqueous and organic phases is enabled

108843/1766

freed by washing out.

The pure diglycidyl ether from DPP has an epoxy equivalent (= gram of resin, which is one gram equivalent Epoxy contain) of 170. In practice, however, the liquid polyglycidyl ethers used according to the Invention of epoxy equivalents of 185 - 210.

The DPP consists essentially of 2,2 -Bis (- ^ hydroxyphenyl) propane, usually in small amounts, e.g. up to 5% by weight of 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane, i.e. the ο, ρ isomer. In general it can The ratio of epichlorohydrin to DPP should be higher, the higher the content of ο, ρ isomers, so that the desired Properties can be achieved according to the invention. Therefore, if a DPP is used that is less than 1% by weight of the ο, ρ isomer, the preferred range of molar ratios is between epichlorohydrin and DPP from 6: 1 to 7: 1. If the DPP contains more than 2, for example 2-4 wt. ^ Of the ο, ρ isomer, the range is from 7: 1 to 8: 1 and with a content of 1-2 wt. # of the ο, ρ isomer from 6.5: 1 to 7.5: 1. Preferably will a DPP is used which contains 2-4 wt. # of the ο, ρ isomer.

1 09 8 Λ 3/1768

The liquid epoxy (B) is selected from the group the glycidyl ester of monocarboxylic acids with at least 12 carbon atoms per molecule, of glycidyl esters of Polycarboxylic acids and glyoidyl ethers of polyhydric alcohols. Suitable glycidyl esters of monocarboxylic acids are those derived from lauric acid, talc fatty acids, WoIlwa ^ c fatty acids, soy fatty acids, ^ Oleic acid, ricinoleic acid and the like are derived.

Glycidyl esters of monocarboxylic acids that contain fewer than 12 carbon atoms per molecule are unsuitable because their volatility value is too high, preference is given to glycidyl esters of straight-chain saturated ones Fatty acids with 12-16 carbon atoms. Examples of glycidyl esters of polycarboxylic acids are the glyoidyl esters of phthalic acid, 'i-'etrahydrophthalic acid, hexahydrophthalic acid, Adipic acid and azelaic acid,

Preferred epoxides (B) are the glyoidyl ethers of polyhydric alcohols, in particular of polyols with at least three alcohol groups per molecule. Examples are the glycidyl ethers of triethylene glycol, tetrapropylene glycol, Glycerine, 1,1,1-trimethylolpropane, pentaerythritol, Hexanetriol and the like. The glycidyl ethers of trihydric alcohols, especially trihydric alcohols, are preferred Alcohols with 3-12 carbon atoms, preferably 1,1,1-trimethylol propane. Glyoidyl ether of lower diols, such as ethylene glycol, are too volatile,

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to use them in the masses according to the invention. The grlyoidyl ethers of polyhydric alcohols in particular have more than one glycidyl group per molecule.

The preparation of the Grlyoidyläther of polyhydric alcohols is illustrated by the following procedure for the preparation of a polyglycidyl ether of 1 ₉ 1,1-trimethylolpropane (DGTMP): g

1 mole of trimethylolpropane-11111 is melted by heating to 60 ⁰ G and 3.9 ml SnGl.zugefügte Over a period of one and a half hours 3MoI epichloro · «· hydrin added at 125 C. After a further reaction time of 3 hours at 125 ⁰ C a clear mixture is obtained which is on 60Grew _o $ diluted with methyl isobutyl ketone. This solution is added at 45 G over two and a half hours to a solution of 3145 mol NaOH in water of 22 Grew. #. After a further one and a half hours at 45 ⁰ C, the organic layer is separated and washed with 500 ml of a 30Grew "# aqueous solution of NaHpPO. washed. The methyl isobutyl ketone is distilled off and the product stabilized 15 mm Hg by heating for half an hour at 150 ⁰ C and then over Hyflo filtered The yield of Polyglycidylather is 75 #, based on trimethylolpropane, the density of 1.13, molecular weight 300, which EpoxydHquivalent 145,

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the viscosity 1.51 Pois at 25 ⁰ C and the volatility value 1o2.

Since the volatility value of the second component (B) is related to the content of volatile impurities such as epichlorohydrin and the solvents used in its manufacture, it is very desirable to stabilize this component before it is mixed with the polyglycidyl ether of DPP, for example by heating over a period of 0 ₉ 2-5 hours at 100 to 200 ^° C. or more, preferably under a vacuum of 100 mm Hg or below.

The volatility values of a number of other stabilized liquid epoxies that have been studied, both within as outside the invention are the following:

Glycidyl ^{ester of 11} VERSATIC "911 (o <-branched monocarboxylic acid, which was obtained by reacting C ₈ -C ^ ₀ olefins ¹ ^ ^co W and H ₂ O in the presence of an acidic catalyst) 74 Glycidyl ester of" VERSATIO ¹¹ 9 (A - branched monocarboxylic acid obtained by reacting Cq olefins with 00 and H ₂ O in the presence of an acidic catalyst 90

ο Glycidyl ester of pelargonic acid ■ »74

oo "··" 2-ethylene hexane carboxylic acid. 100 "ω» ι "» a, a - dimethylvaleric acid ... 101

^ w η η methyl crotonic acid 101

oo "" "lauric acid 22

"Ether" 2-ethylhexanol ~ 1 101

Diglycidyl ether «101

Butyl glycidyl ether ο <> ... _o . _e 103

Phenyl glycidyl ethers _e . _e ... 98

LauryIgIycidylather _c «.. <>. · ..«, ο 37

Vinyl cyclohexene dioxide _o 90

¹¹ EPIKOTIS "812 (polyglycidyl ether of glycerine).».

The component (B) is in the required amount with the liquid polyglyidyl ether of DPP. Component (A) f

mixed to create the base materials according to the invention, preferably with stirring at room temperature or at elevated temperature, for example at temperatures up to 100 ^° C.

Although the general and broadest range in which the addition of a liquid Epoxydkomponente (B) can be used in the inventive compositions, 0 ₈ 5 -. 10 wt $, based on the Polyglycidylather of DPP is, ■ g is clear that the relationship between the volatility value and the viscosity of (B) to the volatility content and the desired viscosity of the preparation in some cases limit this range more narrowly, which is easy with a certain component (B) in connection with a certain component (A) It is clear that a component (B), which has a fairly high volatility value, such as the glycidyl ester of lauric acid (22) in only small amounts (0 _e 5 - 1 wt _e ? 6)

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can be used, while epoxies (B) with low volatility values, such as the preferred glycidyl ethers of trihydric alcohols, used in larger quantities can be. A preferred range for component (B), especially for glyoidyl ethers of trihydric alcohols is 0.75 ~ 5% by weight based on the polyglycidyl ether by DPP »I am the preferred area for the component (B) is from 0.75 to 4 wt. # Based on polyglycidyl ether from

The base materials according to the invention can be used and be mixed with other ingredients, as is known for liquid polyglycidyl ethers from DPP. It can Diluents, solvents, fillers, dyes, plasticizers, stabilizers, other resinous Materials such as vinyl resins, tar, pitch, oils, petroleum « distillates or extracts as well as hardeners such as amines, amides, polycarboxylic acid anhydrides, novolaks, urea-aldehyde resins, Phenol-aldehyde resins, melamine-aldehyde resins and the like for the production of castings, Coatings, adhesives, laminates and the like can be used.

Examples

In the following examples two types of DPP are used, namely DPP I with 3 wt. # Of the o, p-isomer and

109843/1768

DPP II with a content of less than 0.1 wt. # Per o, p-isomers.

The general procedure for making the polyglycidyl ethers from DPP was carried out as follows. The DPP was dissolved in Bpichlorhydrin and, to this solution, which was heated to 70 ⁰ G, increases a 47,5Gew. $ Aqueous solution of NaOH over a period of 3 hours, was added ₉ g while the temperature gradually to 100 ⁰ O. The alkali was added in an amount of 1.95 mol NaOH per mol DPP. After the addition was complete, the reaction mixture was stirred for a further 15 minutes at 100.degree. During the reaction, the added and formed water was removed by azeotropic distillation together with epichlorohydrin, the water layer was separated off and the epichlorohydrin layer was returned to the reactor. The epichlorohydrin was then removed by distillation. & s of toluene was added to a solution of 40 wt. ^ to obtain the resin, which was washed at 45 ⁰ G by stirring for 10 minutes by 1.15 volumes of water per volume of resin solution. After separation of the phases, the solution of toluene and subsequent dehydrohalogenation resin was subjected over a period of 1.5 hours at 85 G with an equal volume of 5 # ig ^it and then for one hour at 45 ⁰ C with 1/3 volume of a 2 wt aqueous NaOH . ^ igen aqueous solution of NaH ₂ PO ^ washed. The toluene was distilled off from the resin solution and the remaining resin

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stabilized by heating for one hour at 170 * 0 and a vacuum of 10 mm Hg. The last was that Resin clarified by adding Hyflo and filtering.

The following table shows the results of a series of tests with different mixing ratios Epichlorohydrin / DPP:

Table I. Example DPP

Molar ratio epichloro-epoxyhydrin / DPP equivalent

Resin shafts

Viscosity volatile poise, 25 ⁰ content (DIN 16945)

a II 10 190 116 0.06 1 II 8th 193 145 0.08 2 II 7th 194 163 0.07 b I. 10 190 130 0 "15 3 I. 8th 194 160 0.16 4th I. 7th 194 190 0 "05 VJl I. 6th 196 232 0 «05

A series of resins produced with Epoxydkomponenten (B) were mixed and ground so that the invention made compositions. The viscosity, the volatility content and the behavior towards crystallization were compared to resins (a) and (b) according to Table I.

and get the following values »

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Table II

770542

Resin according to component example example (B)

Viscosity thick-

the Mi-

schung stop

Poise at (DIN

25 ⁰ G 16945)

Crystallization (days)

a 1Weight ^ GIy-
cidyl laurate 116 2 "Epicote ¹ ·
812 126 2 DGTMP
2.5 weight #
DGTMP + 125 2
b
4th DGTMP ⁺ 150
150
140 4th DGTMP 116 5 155

0 _f 06

0o28

0.20

0.10

0.15 0.10

0.18 0 _f 20

16

29

+ DGTMP »Polyglycidyl ether of 1,1,1-trimethylolpropane.

++ Number of days after which 50 # of the resin ^{had crystallized after storage at 5 0} G (40 g of resin diluted with 5.2 g of n-butylglyoidyl ether and inoculated with 120 mg of crystals of pure diglycidyl ether of diphenylolpropane).

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109843/1

1) $ 45 crystallized

2) 3O # "

3) 1596 "

The mixtures of Examples 2,4,6 and 10 were (based on the mixture) with 1OGew _e $ mixed diethylenetriamine and one day at room temperature and turns · closing at 125 ° G cured. The Barcol hardness of all castings was 30, the Vicat softening temperature at 0.1 mm penetration showed the following values:

114 ° 0 for the resin according to Example 2j

114 ⁰ O in the case of the resin according to Example 4;

112 ⁰ C for the mixture according to Example 6;

112 ⁰ C for the mixture according to the example

Pat ent claims

109843/1768

Claims (1)

177-542 1A-34617 Patent claims 1c base material based on epoxy compounds with a viscosity between 90 and 150 pois «at 25 ° o and a volatility content of less than 0.3% by weight, characterized by a content of (A) a liquid polyglycidyl ether of diphenylol propane, -8 mol equivalents of epichlorohydrin with 1 mol equivalent of diphenylolpropane has been produced in the presence of an alkaline compound, and as the second component (B) 0o5-10% by weight based on the polyglycidyl ether of diphenylolpropane, a liquid epoxide with a viscosity below 20 poise at 25 ⁰ O and a volatility value below 25, the liquid epoxide being selected from the group consisting of the glycidyl esters of monocarboxylic acids with at least 12 carbon atoms per molecule, the glycidyl esters of polycarboxylic acids and the glycidyl ethers of polyhydric alcohols. 109843/1768 _> - l770b42 2. Base material according to claim 1, characterized in that the liquid polyglyoidyl ether (A) has been obtained by reacting 6-7 mol equivalents of epichlorohydrin with 1 mol equivalent of a diphenylolpropane which is less than 1 wt. ⁰ Yes 2- (4-hydroxyphenyl ) -2- (2-hydroxyphenyl) propane. 3. Base material according to claim 1, characterized in that the liquid polyglycidyl ether (A) has been obtained by reacting 6 "5-7o5 mole equivalents of epichlorohydrin with 1 mole equivalent of a diphenylolpropnas, the 1 - 2 wt. ^C / 2- (4 -Hydroxyphenyl) -2- (2-Hydroxyphenyl) propane. 4. Base material according to claim 1, characterized in that the liquid polyglycidyl ether (A) has been obtained with a diphenylolpropane containing more than 2% by weight of 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane contains. 5. Base material according to claim 4, characterized in that the liquid polyglycidyl ether (A) by reacting 7-8 mole equivalents of epichlorohydrin with 1 mole equivalent of diphenylolpropane. 1 09843/1768 6. Base material according to claims 1-5, characterized in that the liquid epoxy (B) is a glycidyl ester of a straight-chain saturated acid with 12-16 carbon atoms per molecule « 7. Base material according to claim 6, characterized in that component (B) 0.5-1 G Glycidyl laurate is " 8. Base material according to claim 1-5, characterized in that component (B) is a Is glycidyl ether of a polyhydric alcohol. 9. Base material according to claim 8, characterized in that the component (Β) is a glycidyl ether of a trihydric alcohol. 10 · Base according to claim 91, characterized in that component (B) is a glycidyl ether a trihydric alcohol with 3-12 carbon atoms per molecule is. - 4 -109843/1768 So 11o base according to claim 10, characterized in that component (B) is a glycidyl ether
of 1, isi-trimethylolpropane is « 12. Base mass according to claim 1 «11, marked e t by a content of 0 «75-4 wt. # of the component ™ (B) ι based on the polyglycidyl ether of diphenylolpropane. 13. A base composition according to claim 1-12, characterized by a content of 0.75 -. ^ 4 weight of component (B), based on the polyglycidyl ethers of diphenylolpropane. 57VI 109843/1768